DE4011927A1 - New di:keto di:hydro-pyrrolo-pyrrole cpds. and di:thio cpds. - for dyeing cellulosic and nitrogenous material, e.g. polyamide - Google Patents

Abstract

Dyeing and printing of nitrogenous and cellulosic fibre materials is carried out with 1,4-diketo- or 1,4-diethio-1,4-dihydro-pyrrolo(3,4-c) pyrrole cpds. of formula (I). In (I) A and B = (het)aryl, at least one of these having a gp. imparting solubility in water; X = O or S; R1 and R2 = H or a (substd.) (cyclo)alkyl or ar(alk)yl gp. New 1,4-dikero-1,4-dihydro-pyrrolo(3,4-c) 3-(4-sulphophenyl)-6- (3-bromo-4-sulphophenyl) cpd. (IA), 3-(4-sulphophenyl)-6-(3,4-dichlorophenyl) cpd. (IB), 3-(chlorophenyl)-, 3-(chloro-sulphophenyl)-, 3-(toyl)- or 3-(sulphotolyl)-6-(chloro-sulphophenyl)- or -6-(sulphotolyl)-cpds. (IC) and 3-(sulphophenyl)-6-(chloro-sulphophenyl)- or -6-methoxy-sulphophenyl)-cpds. (ID) of formulae (IA), (IB), (IC) and (ID). Formulae, = H or a cation. USE/ADVANTAGE - (I) are claimed esp. for dyeing nitrogenous textile fibre materials, partic. synthetic polyamides, and leather. They are suitable for dyeing e.g. rayon, cotton, hemp, leather, paper, nylon 6 and nylon 6,6 e.g. in the form of fibres, yarns, woven and knitted fabrics and carpets. (I) are water-sol. and give yellow to red dyeing with good general fastness.

Description

The present invention relates to the use of water-soluble pyrrolo- [3,4-c] - pyrrole for dyeing nitrogenous and cellulosic fiber materials.

Diketo-pyrrolo-pyrroles are known chemical compounds, for example in the European patent applications no. 00 61 426 and 02 24 445 as pigments for coloring of high molecular weight organic polymers are described.

It has now surprisingly been found that certain pyrrolo [3,4-c] pyrroles excellent for dyeing various nitrogenous and cellulosic Suitable fiber materials and give dyeings with good general fastness properties.

The present invention therefore relates to the use of compounds of formula

wherein A and B are the same or different aryl or heterocyclic aromatic radicals are, of which at least one carries a water-solubilizing group, X for an O- or S atom and R₁ and R₂ are each independently hydrogen or one optionally substituted alkyl, cycloalkyl, aryl or aralkyl radical mean for Dyeing and printing nitrogenous and cellulosic fiber materials.

If A and / or B in the compounds of formula (1) are aryl groups, it is z. B. mono- to tetracyclic, especially mono- or bicyclic radicals, thus for example around 4-biphenylyl or 1- or 2-naphthyl radicals and in particular around  optionally substituted phenyl radicals.

As substituents for the phenyl radical A and / or B come in addition to those below mentioned water-solubilizing groups z. B. in question: C₁-C₄ alkyl, including generally to understand methyl, ethyl, n- or iso-propyl, or n-, iso-, sec- or tert-butyl is; C₁-C₄ alkoxy, with which generally methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy is included; Halogen, e.g. B. fluorine, chlorine or bromine; C₂-C₄ alkanoylamino, e.g. B. acetylamino or propionylamino; Amino; N-mono- or N, N-di-C₁-C₄-alkylamino; Phenylamino; C₁-C₄ alkoxycarbonyl; Nitro; Cyano; Trifluoromethyl; Carbamoyl; Ureido; Hydroxy.

If A and / or B are heterocyclic-aromatic radicals, then preferably mono- to tricyclic radicals which have N, S and / or S as heteroatoms. The hetero- Cyclic-aromatic radicals can be purely heterocyclic or a heterocyclic Ring and one or more fused benzene rings; Examples are: Pyridyl, pyrimidyl, pyrazinyl, triazinyl, furyl, pyrrolyl, thienyl, quinolyl, benzofuranyl, Benzimidazoylyl, benzoxazolyl or benzthiazolyl. The heterocyclic residues can in addition to the water-solubilizing groups mentioned below, e.g. B. the previously for the Phenyl radical A and B bear substituents.

At least one of the radicals A and B, preferably both, have one or more water solubilizing groups; Examples of suitable water-solubilizing Groups are; -SO₃L, -COOL, -PO₃L₂, -CH₂SO₃L, sulfamoyl, N-mono- or N, N-Di-C₁-C₄-alkylsulfamoyl or C₁-C₄-alkylsulfonyl, wherein L is hydrogen or a Cation, e.g. B. an alkali metal cation such as Li⊕, Na⊕ or K⊕ or an ammonium cation, means.

The radicals A and / or B preferably have one as water-solubilizing groups Residue-SO₃L or -COOL and particularly preferably a residue-SO₃L, where L is the has previously given meaning.

The radicals A and B can be different or the same.

A and B independently of one another preferably represent an unsubstituted or z. B. substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, -SO₃L and / or -COOL Phenyl radical, where at least one of the radicals A and B is a group -SO₃L or -COOL  carries and L has the meaning given above.

A and B independently of one another particularly preferably each represent an unsubstituted or phenyl radical substituted by methyl, methoxy, chlorine, bromine and / or -SO₃L, wherein at least one of the radicals A and B carries a group -SO₃L and L the previously has the meaning given.

X preferably represents the O atom.

R₁ and / or R₂ mean an optionally substituted alkyl radical, this can, for. B. an unsubstituted or z. B. by halogen, C₁-C₄ alkoxy, cyano, unsubstituted or phenoxy or C₂-C₄-alkoxycarbonyl substituted by chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy substituted C₁-C₆ alkyl radical.

R₁ and R₂ are each independently preferred as an alkyl radical unsubstituted or substituted by chlorine, fluorine, cyano, methoxy or ethoxy C₁-C₄ alkyl; Examples of substituted alkyl radicals R₁ and / or R₂ are trifluoromethyl, Trifluoroethyl, cyanomethyl or methoxycarbonylmethyl.

Are R₁ and / or R₂ for a cycloalkyl radical, it is z. B. the Cyclopentyl or cyclohexyl.

If R₁ and / or R₂ are an aryl radical, then these apply to the aryl radical A beforehand indicated meanings and preferences.

R₁ and / or R₂ represent aralkyl radicals, then preferably those with 7 to 12 carbon atoms; examples include benzyl and phenylethyl.

The radicals R₁ and R₂ can be different or, preferably, the same.

R₁ and R₂ independently of one another preferably represent hydrogen, unsubstituted or C₁-C₄-alkyl substituted by chlorine, fluorine, cyano, methoxy or ethoxy, Cyclopentyl, cyclohexyl, unsubstituted or by C₁-C₄-alkyl, C₁-C₄-alkoxy, Halogen, sulfo or carboxy substituted phenyl, benzyl or phenylethyl.

Used in a particularly preferred embodiment of the present invention  compounds of the aforementioned formula (1), wherein R₁ and R₂ each Mean hydrogen.

Of particular interest is the use of compounds of the ones specified above Formula (1) in which X denotes an O atom, A and B each independently unsubstituted or by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, -SO₃L or -COOL represent substituted phenyl radical, wherein at least one of the radicals A and B is one or carries two groups -SO₃L or -COOL and L has the meaning given above, and R₁ and R₂ independently of one another hydrogen, unsubstituted or by chlorine, fluorine, Cyano, methoxy or ethoxy substituted C₁-C₄ alkyl, cyclopentyl, cyclohexyl, unsubstituted or by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, sulfo or carboxy substituted phenyl, benzyl or phenylethyl.

Of particular interest is the use of compounds of the formula

in which A ′ and B ′ each independently represent an unsubstituted or methyl group, Methoxy, chlorine, bromine or -SO₃L substituted phenyl radical, at least one of the radicals A 'and B' carries a group -SO₃L and L has the meaning given above Has.

The compounds of formula (1) are e.g. B. from EP-A 02 24 445 or can be produced according to the methods described there.

The compounds of formula (1) are suitable for dyeing or printing of various nitrogenous and cellulosic fiber materials, the generally used methods are used. Suitable nitrogen-containing fiber materials are in particular textile fiber materials, e.g. B. those made of silk, wool or synthetic polyamides; fiber materials made from mixed fibers such as z. B. made of wool / cotton or polyamide / cotton mixed fibers.  

Suitable cellulosic fiber materials are in particular textile fiber materials, e.g. B. made of rayon, cotton or hemp. In addition to the textile substrates, leather and Paper with the impurities (dyes) of the formula (1) are colored.

The compounds of formula (1) are particularly suitable for dyeing synthetic polyamides such as nylon 6 or nylon 6.6.

The textile fiber materials can be in a wide variety of processing states are present, e.g. B. as fiber, yarn, fabric, knitted fabric or carpet.

The compounds of the formula (1) are preferably colored from an aqueous liquor after the exhaust process at temperatures of e.g. B. 20 to 130 ° C and preferably 25th up to 100 ° C. The dyeing time can vary within wide limits; practical is z. B. a time of 15 minutes to 10 hours, preferably 30 minutes to 4 hours. At the Finally, the dye bath is usually cooled and the dyed material rinsed and dried. The dyes of the formula (1) are preferably used alone or in Colored with other dyes; a mixture of various dyes of the formula (1).

In addition to the dye, the dye baths can also contain other conventional additives, e.g. B. network and Defoaming agents, leveling agents, deaerating agents, penetration accelerators or agents influencing the properties of the textile material, e.g. B. plasticizers, Additives for flame retardant or dirt, water and oil repellent agents as well contain water softening agents and natural or synthetic thickeners. As The dye baths can contain further additives, such as mineral acids such as sulfuric acid or phosphoric acid. contain organic acids such as formic, vinegar, citric or oxalic acid. The Acids are used primarily to adjust the pH of the dye liquors.

Furthermore, the dye liquor salts, especially ammonium or alkali salts such as. B. Contain ammonium sulfate, ammonium or sodium acetate or sodium sulfate.

You get level brilliant colorations in z. B. yellow to red tones with good general fastness properties, in particular good rub, wet, wet rub, sweat and light fastness.

The following examples serve to illustrate the invention. Parts and percentages refer to the weight unless otherwise stated. Parts by weight and Volumes are related to each other in the same way as kilograms and liters. The Temperatures are given in degrees Celsius.

Example 1

0.6 parts of the dye of the formula

are dissolved in 450 parts of water, the solution with 0.45 parts of ammonium acetate are added and the pH is adjusted to 5 with acetic acid. In this dye bath at 40 ° C 10 parts of polyamide tricot (Helanca) and then the fleet heated to 100 ° C within 45 minutes. It is dyed at 100 ° C. for 60 minutes and cooled then the dye bath to 70 ° C within 10 minutes. The color obtained is finally rinsed with water and dried; it has a brilliant golden yellow Nuance that is highly fluorescent and good general fastness, in particular Wet fastness properties.

Example 2

The procedure is as described in Example 1, but is used instead of 0.6 part of the dye of the formula (2) 1.0 part of the dye of the formula  

you get a reddish brilliant orange color that is highly fluorescent and good General fastness properties, especially wet fastness properties.

Example 3

The procedure is as described in Example 1, but is used instead of 0.6 part of the dye of the formula (2) 1.2 parts of the dye of the formula

you get a brilliant red color with good general fastness properties.

Example 4

10 parts of cotton fabric (bleached and mercerized) are in at approx. 30 ° C  a dye bath is introduced, which contains 200 parts of water and 0.35 part of the dye formula

contains.

The liquor is heated to 95 ° C. within 30 minutes and at this temperature for 15 minutes Leave temperature. Then 4 parts of Glauber's salt are added and more Colored for 45 minutes at 95 ° C. The dye bath is then opened within 15 minutes Cooled to 80 ° C. and left at this temperature for a further 15 minutes. The Coloring is then rinsed thoroughly with cold water and dried.

Example 5

The procedure is as described in Example 4, but is used instead of that dye used an equivalent amount of the dye of the formula

you get a red, highly fluorescent color, the good general fastness properties having.

Example 6

100 parts of wool knitting yarn are introduced into a dyebath at 50 ° C. 4000 parts of water 2 parts of the dye of the formula  

Contains 3 parts of ammonium sulfate and 2 parts of a leveling aid. The fleet will brought to boiling over 45 minutes and at boiling temperature for 45 minutes held. The material to be dyed is then taken out with cold water rinsed thoroughly and dried. You get a red colored wool with good Authenticity properties.

Example 7

The procedure is as described in Example 6, but is used instead of there dye used an equivalent amount of the dye of the formula

you get a red color with comparable fastness properties.

Examples 8-15

Comparable can be carried out analogously as described in Examples 1 to 7 Dyes on polyamide, wool or cotton using the in the Manufacture dyes mentioned in the table:  

Claims (19)

1. Use of compounds of the formula wherein A and B are the same or different aryl or heterocyclic aromatic radicals, at least one of which carries a water-solubilizing group, X represents an O or S atom and R₁ and R₂ are each independently hydrogen or an optionally substituted alkyl, Cycloalkyl, aryl or aralkyl radical mean for dyeing and printing nitrogenous and cellulosic fiber materials. 2. Use according to claim 1, characterized in that A and B in the compounds of the formula (1) independently of one another each a 4-biphenylyl, 1- or 2-naphthyl or an optionally further substituted phenyl radical. 3. Use according to claim 1 or 2, characterized in that A and B independently one each unsubstituted or by C₁-C₄-alkyl, C₁-C₄-alkoxy, Halogen, C₂-C₄-alkanoylamino, amino, N-mono- or N, N-di-C₁-C₄-alkylamino, Phenylamino, C₁-C₄ alkoxycarbonyl, nitro, cyano, trifluoromethyl, carbamoyl ureido and / or hydroxy substituted phenyl radical and at least one of the radicals A and B additionally carries a water-solubilizing group. 4. Use according to one of claims 1 to 3, characterized in that it the water-solubilizing group is a residue -SO₃L, -COOL, -PO₃L₂, -CH₂SO₃L, sulfamoyl, N-mono- or N, N-di-C₁-C₄-alkylsulfamoyl or C₁-C₄-alkylsulfonyl and L is hydrogen or a cation. 5. Use according to claim 4, characterized in that it is in the water-solubilizing group around a residue -SO₃L or -COOL, preferably -SO₃L, acts and L has the meaning given in claim 4.   6. Use according to one of claims 1 to 5, characterized in that A and B independently of one another each an unsubstituted or by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen -SO₃L and / or -COOL substituted phenyl radical, where at least one of the radicals A and B carries a group -SO₃L or -COOL and L Means hydrogen or a cation. 7. Use according to one of claims 1 to 6, characterized in that A and B independently of one another each unsubstituted or by methyl, methoxy, chlorine, Bromine and / or -SO₃L substituted phenyl radical, at least one of the Residues A and B carries a group -SO₃L and L is hydrogen or a cation. 8. Use according to one of claims 1 to 7, characterized in that X for the O atom stands. 9. Use according to one of claims 1 to 8, characterized in that R₁ and R₂ independently of one another hydrogen, unsubstituted or by chlorine, fluorine, Cyano, methoxy or ethoxy substituted C₁-C₄ alkyl, cyclopentyl, cyclohexyl, unsubstituted or by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, sulfo or carboxy substituted phenyl, benzyl or phenylethyl. 10. Use according to one of claims 1 to 9, characterized in that R₁ and R₂ each represent hydrogen. 11. Use of compounds of formula (1) according to claim 1, wherein X is a O atom means that A and B are each independently an unsubstituted or through C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen, -SO₃L and / or -COOL substituted phenyl represent, wherein at least one of the radicals A and B is a group -SO₃L or -COOL carries and L is hydrogen or a cation, and R₁ and R₂ independently Hydrogen, unsubstituted or substituted by chlorine, fluorine, cyano, methoxy or ethoxy C₁-C₄-alkyl, cyclopentyl, cyclohexyl, unsubstituted or by C₁-C₄-alkyl, C₁-C₄ alkoxy, halogen, sulfo or carboxy substituted phenyl, benzyl or phenylethyl mean for dyeing and printing and cellulosic nitrogenous Fiber materials.   12. Use according to claim 11 of compounds of the formula wherein A 'and B' each independently represent an unsubstituted or substituted by methyl, methoxy, chlorine, bromine and / or -SO₃L, where at least one of the radicals A 'and B' carries a group -SO₃L and L is hydrogen or a cation is. 13. Use according to one of claims 1 to 12 for dyeing nitrogenous textile fiber materials and leather. 14. Use according to claim 13 for dyeing synthetic polyamides. 15. Process for dyeing nitrogenous and cellulosic fiber materials, characterized in that a compound of formula (1) according to claim 1 used. 16. Compound of the formula where L is hydrogen or a cation. 17. Compound of the formula where L is hydrogen or a cation. 18. Compounds of the formula where L is hydrogen or a cation. 19. Compounds of the formula where L is hydrogen or a cation.